Production of high molecular hydroxylated condensation products from crotonaldehyde



Patented Oct. 31, 1939 UNITED STATES PRODUCTION OI DROXYLATED HIGHMOLECULAR HY- CONDENSATION rsonswam];

UC'I'S FROM CBOTQN Willi Schmidt, Julius Bothhaas, Lad

Thowalt, and Alexander wigshai'en-on-thc-Bhino, Germany, minors to I. G.Far-benindustrie Akticnxeeollsolnft,

many

Frankfort-on-thc-Main, Gor- No Drawing. Application October 18', 1987,,Be-

In Germany Oct rial No. 189,518. 1938 dclaims.

The present invention relates to an improved process of producing highmolecular hydroxylatcd condensation products from orotonaidehyde.

We have round that high molecular hydroxyl- 5 steel condensationproducts are obtained by condensing crotonaldehyde or aldehydes capableof conversion into the same either alone or in admixture with substanceshaving removable hydrogen atoms and/or reactive double linkages m in thepresence of alkali alcoholates as condensing agents and catalyticallyhydrogenating the resulting condensation products, As aidehydes whichare capable of being converted into crotonaldehyde there may bementioned acetaldehyde g and side]. Mixtures of acetaldebyde, aldoland/or crotonaldehyde may also be used for the process. As substanceshaving removable hydrogen atoms or reactive double linkages, which maytake part in the condensation, there may 30 be mentioned acetone, methylethyl ketone,

methyl vinyl ketone, cyolopentanone, cyclohexanone, formaldehyde,isobutylene, diisobutylene, monomeric vinyl compounds, such as vinylethers, vinyl esters, acrylic esters, acrylic nitrile, and

, also maleic and phthalic acid derivatives. By adding these reactivecompounds to the condensation mixture, the properties of the alcoholsobtained are changed. Thus for example from a mixture of acetone and apreponderating amount of crotonaldehyde there is obtained according tothis invention a brittle resin, externally similar to colophony. whichcontains ester groups in addition to hydroxyl groups, tainedfromcrotonaldehyde alone are viscous and sticky and have only a lowsaponiiication value. 1

As condensing agents it is preferable to use alcoholic solutions ofalkali alcoholates, as for example solutions of sodium methylate,potassium methylate, lithium methylate, sodium ethylate, sodiumbutylate, monoand di-sodium glycolate in methanol, ethanol, butanol orother alcohols. The alcoholic solutions used need not be entirely freefrom water. For example solutions of sodi- L um hydroxide or potassiumhydroxide in methan'ol may be used. The said condensing agents act best,however, in the absence of water.

The condensation is preferably carried out by adding the condensingagent to the aldehyde or the mixture containing the aldehyde. Thesidehyde or the mixture containing the aldehyde may, however, be addedto a solution of the condensing agent. It is advantageous not tointroduoe the whole of the aldehyde and condensing agentto be used intothe reaction vessel at once,

while the alcohols obobcr 28.

but only a part thereof, the remainder being in troduced in portions. Inthis way the condensation, which takes place with strong evolution ofheat, is prevented from proceeding too turbulently. If necessary thereaction must be rendered milder by cooling if it proceeds tooturbulently. It is advantageous not to allow the reaction mixture torise to a temperature substantially above 100 C.; the condensation mayalso be carried out, if desired, under pressure. The reaction proceedsextremely rapidly. It is therefore pos+ sible to carry it outcontinuously. Thus for example the alcoholic solution of the alcoholateand the aldehydemay iiow together into a vertical pressure-tight towerand trickle down over filler bodies.

The condensation product is red-yellow in color and of an oily nature.It may be hydrogenated directly but it is preferably to lead carbondioxide in and to separate the carbonate thus formed before thehydrogenation.

The hydrogenation is carried out in the liquid phase with knownhydrogenation catalysts such as are used for example for the hardeningof fats and oils and the reduction of carboxylic acids to thecorresponding alcohols. Suitable hydrogenation catalysts are for examplenickel, cobalt, copper, and precious metals or salts or oxides of thesame or mixtures of the same. The said catalysts may also be depositedon carriers and they may also contain diflicultly reducible orunreducible metal oxides. The hydrogenation should, if possible, becarried out below 250 C. It is therefore frequently of advantage to usehigh hydrogen pressures.

When the hydrogenation is completed, the catalyst is separated in caseswhen the hydrogenation has not been carried out with a rigidly arrangedcatalyst. The resulting colo'rless to pale yellow hydrogenation productis freed from alcohol, which was contained in the condensing agent, andsmall amounts'of readily volatile products by heating. The alcohols ofhigh molecular weight thus obtained are comparatively unitary products.

Example 1 A solution of 50 parts of sodium in 400 parts "product is oimethanol is slowly dropped into. a solution 01 1500 parts oicrotonaldehyde and 1500 parts oi methanol while cooling to about 10below zero C. and while stirring vigorously. The reaction mixturebecomes dark red and the temperature rises to about 40 C. Towards theend the addition oi the sodium methylate. the temperature ialls again.The whole is then stirred ior 2 hours at room temperature withoutcooling. Carbon dioxide is then led into the reaction mixture and, aiterallowing to stand ior several hours, the precipitate iormed isilltered'oii by suction. Aiter the separation oi the alkali carbonate,the reaction mixture is considerably paler. It is hydrogenated with 2.5per cent by weight oi a nickel catalyst activated with chromium at 150C. under a pressure oi 200 atmospheres oi hydrogen, The irced iromcatalyst by filtration and irom methanol by heating, the whole thenbeing heated to irom 200 C. to 300 C. under a pressure oi 2.5millimeters (mercury gauge). '70 parts oi a viscous oil distil over at185 C. The residue consists oi about 1000 parts oi a pale yellow,sticky,

- viscous resin having the iollowing characteristics:

acid vaiue='0, saponiiication value=7.2, hydroxyl value=l65 and iodinevalue=62.8.

Example 2 1400. parts oi crotonaldehyde are allowed to flow into aboiling mixture oi 1160 parts oi acetone and a solution oi parts oisodium in 242 parts oi butanol. when the turbulent reaction iscompleted, a further solution oi 10 parts oi sodium-in 242 parts oibutanol and a iurther 1400 parts oi crotonaldehyde are added. Aiter 2hours, carbon dioxide is led into the reaction mixture and aiterallowing to stand ior several hours the precipitate iormed .is filteredoil. The reaction product is hydrogenated as described in Example 1. Thebutanol and the readily volatile products iorrned are distilled of! upto 156 C. under a pressure at 1 millimeter (mercury gauge). 2777 partsoi a strong brittle resin having an acid value ci 0, a saponiiicationvalue oi 148, a hydroxyl value oi 145 and an iodine value oi 66.3 areobtained.

Example 3 A solution oi parts of sodium in 100 parts oi methanol isallowed to flow slowly into a mixture,

cooled to about 10 below zero C., oi 140 parts oi crotonaldehyde, 49parts '0! maleic anhydride and 190 parts oi methanol while furthercooling.

When the reaction is completed, cooling is discontinued and the reactionmixture slowly heated to about 90 C. Carbon dioxide is then led into thehot solution; the solution is allowed to cool ior some hours and settle,and the precipitate iormed is filtered oil. The reaction product ishydrogenated in the manner described in Example, 1. The hydrogenatedproduct is ireed irom catalyst and volatile constituents and a pale,salve-like product is obtained having the following characteristics:acid value=0, saponiiication value=76.3, hydroxyl value239 and iodinevalue=18.5.

By a corresponding treatment,

(a) 140 .parts oi crotonaldehyde and 74 parts oi 'phtbalic anhydrideyield, when using 15 parts oi sodium, an almost colorless, soit resinhaving an acid value oi 1.9, a saponiiication value oi 20, a hydroxylvalue oi 202 and an iodine value oi 23.2,

(b) 140 parts oi crotonaldehyde, 49 parts oi cyclohexanone and 5 partsoi sodium yield a was is) 140 parts oi crotonaldehyde, 50 parts oiproceeds hard, golden yellow resinhavlz-e acid. value oi 0, asaponincation value or 11.0, a hydronl value oi 174 and an iodine valueoi 56.4,

(c) 140' parts oi crotonaldehyde, 36 parts oi methyl ethyl ketone and 5-parts oi sodium yield a dark, solid resin having an acid value o! 0, asaponiilcation value oi 7.36, a hydroxyl value oi 161 and an iodinevalue oi 46.3,

acrylic acid ethyl ester and 5 parts oi sodium yield a soit, almostcolorless, pasty product having an acid value oi 0, a saponiilcationvalue oi 13, a hydroxyl value oi 300 and an iodine value oi 28.1,

(c) 140 parts oi crotonaldehyde, 36 parts oi vinyl ethyl ketone and 5parts oi sodium yield a pale, hard resin having an acid value oi 0,asaponification value oi 4.6, a hydroxyl value oi 182 and an iodinevalue oi 42.7,

(I) 140 parts oi crotonaldehyde, 57 parts oi d1- isobutylene and 5 partsoi sodium yield a pale, hard resin having an acid value oi 0, a saponi--ilcationvalue of 2.8, a hydroxyl value oi 190 and an iodine value oi45.6, and

(a) 140 parts oi crotonaldehyde, 47 parts oi phenol and 15 parts orsodium yield a golden yellow, solid resin having an acid value oi 0, asaponiilcation value oi 2.5, a hydroxyl value oi 198 and an iodine valueof 47.1.

The relative proportions oi the initial materials so may be variedwithin wide limits.

Example 4 A solution oi 10 parts of sodium hydroxide in 100 parts oimethanol is added in small portions to a cooled solution oi 140 parts oicrotonaldehyde in 100 parts oi methanol. The temperature rises by aboutC. In order to complete the reaction, the whole is boiled ior an hour onthe waterbath.

Aiter treatment with carbon dioxide, the reaction product ishydrogenated in the manner described in Example 1. A pale, somewhatsticky resin is obtained having an acid value of 0, a saponiilcationvalue of 6.7, a hydroxyl value oi 177 and an iodine value oi 60.5.

Example 5 A solution oi 5 parts oi sodium in 50 parts oi methanol isallowed to drop into a mixture oi 140 parts oi crotonaldehyde, 60 partsof para- Example 6 6 A solution oi 15 parts or in 250 parts oi methanolis added in small portions to a mixture oi 140 parts oi crotonaldehyde,47 parts of phenol, 30 parts oi paralormaldehyde and parts oi methanol.when the reaction,

turbulently, is completed, the whole is heated ior an hour on thewaterbath and the reaction product treated with carbon dioxide andhydrogenated. A pale, brittle resin is obtained having an acid value oi0, asaponiilcation value 1 ct 6.8, a hydroxyl value oi 207 and an iodinevalue oi 44.1. I

I! the reaction mixture also contains 57 parts of di-isobutylene,thereis obtained by the same treatment a pale, very male resinhaving'a'n which a Example 7 140 parts oi crotonaldehyde are allowed toflow slowly without cooling into a solution oi parts oi sodium in 240parts oi methanol. The reaction mixture becomes dark brown in colorwhile boiling vigorously under a reflux condenser. The condensationproduct obtained is dark, resinous and sticky. It dissolves in a mixtureoi 200 parts oi methanol and 100 parts oi cyclohexane. Aiter treatingthis solution with carbon dioxide, hydrogenating and removing the lowboiling constituents, a dark yellow, somewhat sticky resin is obtainedhaving an acid value oi 0, a saponiflcation value oi 4.2, a hydroxylvalue oi 208 and an iodine value oi 63.8.

What we claim is:

1. In the process oi producing high molecular hydroxylated condensationproducts from crotonaldehyde the step which comprises condenslngcrotonaldehyde by means of alkali alcoholates and hydrogenating theresulting condensation products.

2. In the process at producing high molecular hydroxylated condensationproducts irom crotonaldehyde the step which comprises condensing analdehyde capable oi being converted into crotonaldehyde by means oialkali alcoholates and hydrogenating the resulting condensationproducts.

3. In the process oi producing high molecular hydroxylated condensationproducts from crotonaldehyde the step which comprises condensing amixture 01' a preponderating amount of crotonaldehyde and a substanceselected from the group consisting of. aldehydes, ketones, and phenolsby means oi alkali alcoholates and hydrogenating the resultingcondensation products.

4. In the process of producing high molecula hydroxylated condensationproducts from crotonaldehyde the step which comprises condensingcrotonaldehyde by means oi alkali alcoholates at temperatures not risingsubstantially above '100 C. and hydrogenating the resulting condensationproducts.

WILLI SCHMIDT. JULIUS THEWALT. ALEXANDER ROTHHAAB.

